Light-sensitive photographic element having a light-absorbing layer



1952 A. E. VAN DORMAEL ETAL 2,

LIGHT-SENSITIVE PHOTOGRAPHIC ELEMENT HAVING A LIGHT ABSORBING LAYER Filed Nov. 14, 1947 FIG. 8

o EMULSION SUPPORT F|LTER LAYER CONTAINING UNSYMMETRICAL OXONOL DYE a EMULSION fi FILTER LAYER CONTAINING UNSYMMETRICAL OXONOL DYE b \-suPPoRT EMULSION CONTAINING UNSYMMETRICAL OXONOL DYE b- \SUPPORT INVENTORS ANDRE EMILE VAN DORMAEL LAURENT ALOYS VAN DER AUWERA following scheme:

Patented Dec. 9, 1952 UNITED 'S TAT-ES ATENT OFFICE LIGHT- SENSITIVE PHOTOGRAPHIC ELE- MENT HAVING A LIGHT-ABSORBIN G LAYER Andr Emile van Dormael, fieverlee-Louvain, and

Laurent Aloys van der Auwera,:Mortsel.-:Ant- Werp, Belgium, assig'nors .to Gevaert-.l.hoto- Producten N. V., Mortsel-Antwerp, -Belgium,-.a

company of Belgium ,Application November 14, 1947;"Serial No. 786,152 InlGreat Britain November 22, 1946 10 Claims.

This .invention relates to; photographic. material comprising colored" layers, especially ,antihalation or"filter.layers, and to" its manufacture. "Photographic material often comprises one or moreilayers "containing dyestuffs. *Suchilayers,

which may be light-sensitive or non 'lighti-sensitive layers of water-soluble colloids, such asgela- Ltine, "serve, the purpose of reducing 'halation; or

producing afiltering action on the exposure light either in the cameraor whilst printing or employed for fogging residual silver saltin reversal.

As dyestu'fisfor filter or anti-halation layers in photographic materials, it'has been proposed to use symmetric oxonol dyestufis corresponding to the following general formula:

o='oc=cnon=crr cn=cno \Z/ \Z/ wherein Z is the atoms necessary to.complete a heterocyclic nucleus.

O-OH An' object 'ofjour' present invention is 'to -provide "new colored photographic layers.

Another object "of our invention. is to provide new photographic materials comprising colored "photographic layers.

Aifurther object or this invention is to,provide :a process for the manu'facturebf such 'mate- :ria1s.

"Still further objects will appear. from'thefollowing. description.

*The foregoing-and all the objects, which will hereinafter appear, are accomplished by applying to a photographic support or layer .a layer containing an asymmetric oxonol dyestu'ff according to'the following general formula:

\ZI wherein Z.and.Z are .the atoms necessary to complete different heterocyclic nuclei.

These new dyestuffs may be prepared, among other processes, by a method indicated by the silver; halide emulsions iont'a support,;.the..dyestuffbeing incorporated :either in the emulsion-layers or in'separate colloidl'ayers.

The. specification is accompaniedlby audrawing' iniwhich:

Fig.' 1 illustrates a .photographicsxelement em- .bodying: features of ourhzinvention';

Fig. 2 "illustrates a .modifiedtphotographic element; and

Fig. '3 illustrates J anotherzmodification.

Referring to "the: drawing, .inLFigs; 1.:.'and;2,. a designates an emulsion, b.a,-.support,'andizc:a filter or antihalationlayer. In Fig. 1, the filter layer is shown as a backing. In the embodiment of Fig. "2, thefilter layer is interposed between the emulsiontandiithe support. .In Fig..3,;ac is an emulsion layer, having incorporated therein filter or antihalation substance, this layer/being applied'to the supporting layer b.

The photographic materials according to the present invention mayv include asupportof. any

suitable transparent material, such as glass,-cellulose ester. or synthetic resin.

'The, following specific examples will illustrate our invention more clearly without limiting, however, its scope.

"Example 1 2.5 g. of the dyestuff of the: following; formula:

dissolved .in '200 .cm'. ,alcohol, are AaddedUto, '800 cm. ..of clan .aqueous ,cgelatine solution zcontaining '8 gr gelatine per 100 cm. v of water. After spreading this solution upon the back of a photographic material, a purplish-red layer is obtained.

The dyestuff may be obtained as follows: 5 g. 4 -(w anilido A 2:4 pentadienylidene)- 1- phenyl-S-methyl-5-pyrazolone and 3 g. N-methyl-rhodanine are dissolved in 30 cm. pyridine and are refluxed for 3 hours in the presence of 6.5 cm. triethylamine. After cooling, the dyestuff is precipitated with ether. Melting point is 230 C. (with decomposition).

The intermediate product mentioned herein may be prepared in the following way: 5.25 g. 1-phenyl-3-methyl-5-pyrazolone and 8.55 g. glutacondialdehyde-dianilide-hydrochloride are refluxed for 3 minutes on the water bath in 60 cm. absolute ethyl alcohol in the presence of 4.2 cm. triethylamine. After cooling, the precipitated product is filtered and recrystallized from ethyl alcohol. Melting point is 185-187 C.

Example 2 2 g. of the dyestuff of the following formula:

=CC=CH--CE=CHOH=CH-C=C-OH l I O=C NH W dissolved in 160 cm. alcohol, are added to 900 cm. of an aqueous gelatine solution containing 8 g. gelatine per 100 cm. water. After spreading this solution upon the back of a photographic material, an intense purple-red layer is obtained.

This dyestuif may be prepared as follows: 5 g. 4 (w anilido A 2:4 pentadienylidene) 1 phenyl-3-methyl-5-pyrazolone (the preparation has been described in the foregoing example) and 3 g. thiobarbituric acid in 30 cm. pyridine are refluxed for 30 minutes in the presence of 6.5 cm. triethylamine. After cooling, the dyestuff formed is precipitated with ether and recrystallized from alcohol. Melting point is at 240 C. (under decomposition).

Example 3 2 g. of the dyestuif of the following formula:

O=CC=CHCE=CHCH=CHC=COH Hie-N s o=c NH o HNC=S HaC-N II B and 6 g. thiobarbituric acid are dissolved in 60 cm. pyridine and refluxed for 30 minutes in the presence of 14 cm. triethylamine. After cooling, the reaction mixture is precipitated with ether and recrystallized from alcohol. is 180 C. (with decomposition).

The intermediate product mentioned herein is obtained in the following way: 7.5 g. N-methylrhodanine and 14 g. glutacondialdehyde-dianilide-hydrochloride are dissolved in cm. of absolute ethyl alcohol and refluxed for 5 minutes on the water bath in the presence of '7 cm. triethylamine. After cooling, the precipitated product is filtered and recrystallized from alcohol. Melting point is at 205 C.

Example 4 2 g. of the dyestuif of the following formula:

O=CC=CHCH=CHC H=CH-C=COH HsC-N Melting point Example 5 2 g. of the dyestulf of the following formula:

0=OC=Cl1CH=CHCH=CH- =C-OH dissolved in cm. alcohol, are added to 900 emf of a gelatine solution containing 8 g. gelatine per 100 cm. water. After spreading this solution upon the back of a photographic material, an intense purple-red layer is obtained.

This dyestuff may be prepared in the following way: 10 g. 5-(w-anilido-A-2:4-pentadienylidene) 3-methyl-rhodanine (described in Example 3) and '7 g. N-phenyl-rhodanine are dissolved in 70 cm. pyridine and refluxed for 3 hours in the presence of 14 cm. triethylamine. After cooling, the product is precipitated with ether. Melting point is 113 C. (with decomposition).

We claim:

1. Photographic element comprising a support having thereon a light-sensitive silver halide emulsion layer and a colored layer containing an asymmetric oxonol dyestuff according to the general formula: o=q-- 9=cHcH=oHcH=cH-cc-o ]n wherein Z and Z are different and represent the atoms necessary to complete a member selected from the group consisting of l-phenyl-3-methyl- 5-pyrazolone, l-(p-sulphophenyl)-3-methyl 5- pyrazolone, N-methyl-rhodanine, N-phenyl-rhodanine, and thiobarbituric acid.

2. Photographic element comprising a support 'ifhaving thereon "a ligh-t-sensitlve-s'ilver halide -l emulsion ;layer and a filter layer containingan "asymmetric oxonol dyestuif according to the general formula:

1 wherein Z and Z are different and represent the .atomsnecessary to complete 'a member'tselected tifromthegroup consisting pf laphenyl 'semethyl- "5'5pyrazolone; l--('p-=sulphophen"yl) -3-meth'yl -:'*5- .ipyrazolone, N-methyl-"rhodanine, N-phenyl rho- :danine, and "'thiobarbituric acid.

"'3. Photographic element comprising :a support having thereon -a light-sensitive silver halide emulsion layer and an anti-halation layer containing an asymmetric oxonol dyestufi according to the general formula:

wherein Z and Z are different and represent the atoms necessary to complete a member selected from the group consisting of 1-phenyl-3-methyl- 5-pyrazolone, l-(p-sulphophenyl)-3-methyl 5- pyrazolone, N-methyl-rhodanine, N-phenyl-rhodanine, and thiobarbituric acid.

.4. Photographic element comprising a support having thereon a light-sensitive silver halide emulsion layer and an anti-halation layer containing an asymmetric oxonol dyestuff according to the general formula:

wherein Z represents the atoms necesary to complete a member selected from the group consisting of 1phenyl-3-methyl-5-pyrazolone, and 1- (p-sulphophenyl)-3-methyl-pyrazolone, and Z represents the atoms necessary to complete a member selected from th group consisting of N-methyl-rhodanine, N-phenyl-rhodanine, and thiobarbituric acid.

\6 taming-an: asymmetric oxonoldyestufiraccording to the general formula:

wherein Z represents the atoms necessary to com- ,,plete* a member selected from the group. consisting ofyN-methyl-rhodanine, and N-phenylrhodanine, and Z represents the atoms necessary to complete a member selected from the group consisting of 1-phenyl-3-methyl-5-pyrazolone, 1- (p-isulphophenyl) +l3=methyl-5-pyrazolone, Wand "thiobarbitu'ric':acid.

fz'fi rPhotographicrelement'zcomprisingtassumiort emulsion layer and an anti-halation layer containing an asymmetric oxonol dyestufl according to the general formula:

8. Photographic element comprising a support having thereon a light-sensitive silver halide emulsion layer and an anti-halation layer con- ,taining an asymmetric oxonol dyestufi accord- 0 ing to the formula:

mi legs Ht HaC-N 5. Photographic element comprising a support having thereon a light-sensitive silver halide IL SOaH H 9. Photographic element comprising a Support having thereon a light-sensitive silver halide emulsion layer and an anti-halation layer 0011- 75 emulsion layer and an anti-halation layer conhaving i thereon ca. light-sensitive Jl$fl3leri halide taining an asymmetric oxonol dyestufi according to the formula:

10. A photographic element comprising a support having thereon at least one photosensitive silver halide emulsion layer and a light absorbing layer containing a dye having the formula:

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,032,506 Schneider Mar. 3, 1936 2,036,546 Schneider Apr. '7, 1936 2,220,123 Schwarc Nov. 5, 1940 2,241,238 Brooker et a1. May 6, 1941 2,274,782 Gaspar Mar. 3, 1942 2,345,193 Gaspar Mar. 28, 1944 

1. PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AND A COLORED LAYER CONTAINING AN ASYMMETRIC OXONOL DYESTUFF ACCORDING TO THE GENERAL FORMULA: 